(E)-Methyl 2-[(2S,3S,12bR)-3-ethyl-8-meth-oxy-1,2,3,4,6,7,12,12b-octa-hydro-indolo[2,3-a]quinolizin-2-yl]-3-methoxy-acrylate ethanol solvate.

In the title compound, C(23)H(30)N(2)O(4)·C(2)H(6)O, the indole derivative has four fused rings, forming an indolo[2-3a]quinolizine system, in which one six-membered ring is directly connected to the indole unit and has a distorted chair conformation. The fourth ring is also a six-membered ring, depicting a regular chair conformation. In the crystal, the mol-ecules are linked by N-H⋯O and O-H⋯N inter-actions, forming a C(7) chain.

Related literature

For previous crystallographic analysis of mitragynine salts (hydro­bromide and hydro­iodide), see: Zacharias et al. (1965 ▶). For the method of extraction, see: Ponglux et al. (1994 ▶). For synthetic studies, see: Ma et al. (2009 ▶). For medicinal properties, see: Boyer et al. (2008 ▶); Weibrecht et al. (2008 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C23H30N2O4·C2H6O

M = 444.56

Orthorhombic,

a = 7.60450 (10) Å

b = 11.7534 (2) Å

c = 26.5735 (4) Å

V = 2375.11 (6) Å3

Z = 4

Cu Kα radiation

μ = 0.70 mm−1

T = 100 K

0.12 × 0.09 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: none

34365 measured reflections

4158 independent reflections

3649 reflections with I > 2σ(I)

R int = 0.083

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.089

S = 1.05

4158 reflections

295 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.18 e Å−3

Absolute structure: Flack (1983 ▶), 1758 Friedel pairs

Flack parameter: 0.2 (2)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and ORTEP-3 (Farrugia, 1997 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017309/bx2206sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017309/bx2206Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C23H30N2O4·C2H6O	F(000) = 960
Mr = 444.56	Dx = 1.243 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3152 reflections
a = 7.6045 (1) Å	θ = 3.3–64.6°
b = 11.7534 (2) Å	µ = 0.70 mm−1
c = 26.5735 (4) Å	T = 100 K
V = 2375.11 (6) Å3	Needle, colourless
Z = 4	0.12 × 0.09 × 0.06 mm

Bruker APEXII CCD diffractometer	3649 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.083
graphite	θmax = 66.4°, θmin = 3.3°
φ and ω scans	h = −9→9
34365 measured reflections	k = −13→13
4158 independent reflections	l = −31→31

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036	H-atom parameters constrained
wR(F2) = 0.089	w = 1/[σ2(Fo2) + (0.0469P)2 + 0.2771P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
4158 reflections	Δρmax = 0.19 e Å−3
295 parameters	Δρmin = −0.18 e Å−3
0 restraints	Absolute structure: Flack (1983), 1758 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.2 (2)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C3	0.3530 (3)	0.08591 (16)	0.79611 (7)	0.0226 (4)
H3	0.2920	0.0127	0.7987	0.027*
C2	0.3100 (3)	0.13687 (16)	0.74583 (7)	0.0224 (4)
C14	0.2990 (3)	0.15900 (16)	0.84110 (7)	0.0224 (4)
H14A	0.1750	0.1778	0.8388	0.027*
H14B	0.3657	0.2293	0.8412	0.027*
C5	0.6061 (3)	0.00338 (18)	0.75273 (7)	0.0269 (5)
H5A	0.5360	−0.0647	0.7479	0.032*
H5B	0.7275	−0.0197	0.7574	0.032*
C16	0.2800 (3)	0.14709 (17)	0.93877 (7)	0.0237 (4)
C21	0.5794 (3)	−0.00691 (16)	0.84300 (7)	0.0245 (4)
H21A	0.7032	−0.0267	0.8439	0.029*
H21B	0.5124	−0.0769	0.8405	0.029*
C20	0.5303 (3)	0.05433 (16)	0.89183 (7)	0.0228 (4)
H20	0.5406	−0.0014	0.9191	0.027*
C7	0.4161 (3)	0.13592 (16)	0.70469 (7)	0.0234 (4)
C11	0.0631 (3)	0.29780 (17)	0.60685 (8)	0.0301 (5)
H11	−0.0215	0.3322	0.5867	0.036*
C17	0.2551 (3)	0.25695 (16)	0.94916 (7)	0.0257 (4)
H17	0.2198	0.2764	0.9815	0.031*
C8	0.3190 (3)	0.19029 (16)	0.66512 (7)	0.0231 (4)
C10	0.2287 (3)	0.27195 (17)	0.58613 (7)	0.0281 (5)
H10	0.2523	0.2904	0.5528	0.034*
C6	0.5923 (3)	0.07864 (19)	0.70579 (8)	0.0286 (5)
H6A	0.6847	0.1355	0.7063	0.034*
H6B	0.6070	0.0325	0.6758	0.034*
C15	0.3348 (3)	0.09212 (16)	0.88976 (7)	0.0226 (4)
H15	0.2658	0.0220	0.8871	0.027*
C9	0.3566 (3)	0.21944 (17)	0.61479 (7)	0.0246 (4)
C13	0.1537 (3)	0.21960 (17)	0.68469 (7)	0.0241 (4)
C12	0.0231 (3)	0.27357 (17)	0.65616 (7)	0.0281 (4)
H12	−0.0856	0.2921	0.6699	0.034*
C19	0.6535 (3)	0.15316 (18)	0.90462 (8)	0.0268 (4)
H19A	0.6527	0.2068	0.8769	0.032*
H19B	0.6081	0.1923	0.9340	0.032*
C18	0.8419 (3)	0.1177 (2)	0.91491 (9)	0.0359 (5)
H18A	0.8946	0.0905	0.8844	0.054*
H18B	0.8432	0.0583	0.9397	0.054*
H18C	0.9071	0.1819	0.9272	0.054*
C24	0.2472 (3)	0.06448 (17)	0.98062 (7)	0.0245 (4)
C22	0.5687 (3)	0.2261 (2)	0.54835 (8)	0.0362 (5)
H22A	0.5535	0.3068	0.5450	0.054*
H22B	0.4941	0.1875	0.5247	0.054*
H22C	0.6892	0.2066	0.5418	0.054*
C25	0.2001 (4)	0.0389 (2)	1.06740 (8)	0.0398 (6)
H25A	0.2861	−0.0208	1.0688	0.060*
H25B	0.0856	0.0065	1.0623	0.060*
H25C	0.2013	0.0808	1.0984	0.060*
C23	0.2173 (4)	0.45082 (18)	0.93323 (9)	0.0393 (6)
H23A	0.2795	0.4710	0.9634	0.059*
H23B	0.0936	0.4468	0.9402	0.059*
H23C	0.2384	0.5073	0.9079	0.059*
C27	0.7975 (3)	0.33626 (19)	0.79406 (9)	0.0404 (6)
H27A	0.6948	0.3492	0.8149	0.048*
H27B	0.7713	0.3627	0.7603	0.048*
C26	0.9507 (4)	0.4008 (2)	0.81476 (12)	0.0505 (7)
H26A	1.0519	0.3881	0.7939	0.076*
H26B	0.9750	0.3752	0.8484	0.076*
H26C	0.9235	0.4806	0.8153	0.076*
N2	0.5446 (2)	0.06406 (13)	0.79818 (6)	0.0223 (4)
N1	0.1505 (2)	0.18655 (14)	0.73471 (6)	0.0237 (4)
H1	0.0642	0.1955	0.7552	0.028*
O5	0.83716 (18)	0.21863 (12)	0.79292 (5)	0.0297 (3)
H5	0.7462	0.1818	0.7960	0.045*
O3	0.2266 (2)	−0.03588 (11)	0.97486 (5)	0.0323 (3)
O2	0.2782 (2)	0.34155 (11)	0.91554 (5)	0.0303 (3)
O1	0.52291 (19)	0.19211 (12)	0.59849 (5)	0.0310 (3)
O4	0.2410 (2)	0.11472 (11)	1.02612 (5)	0.0343 (4)

	U11	U22	U33	U12	U13	U23
C3	0.0226 (10)	0.0251 (10)	0.0201 (9)	0.0001 (8)	0.0008 (9)	0.0000 (8)
C2	0.0197 (10)	0.0247 (10)	0.0226 (9)	−0.0004 (8)	−0.0025 (8)	−0.0016 (8)
C14	0.0200 (10)	0.0273 (10)	0.0200 (9)	0.0005 (8)	−0.0001 (8)	−0.0007 (8)
C5	0.0234 (11)	0.0319 (11)	0.0253 (10)	0.0065 (9)	−0.0002 (8)	−0.0038 (8)
C16	0.0182 (10)	0.0317 (10)	0.0213 (9)	−0.0008 (8)	0.0002 (8)	−0.0010 (8)
C21	0.0229 (10)	0.0281 (10)	0.0226 (10)	0.0029 (8)	−0.0003 (8)	0.0007 (8)
C20	0.0224 (11)	0.0282 (10)	0.0177 (9)	0.0038 (8)	−0.0005 (8)	0.0026 (8)
C7	0.0236 (10)	0.0263 (10)	0.0204 (9)	−0.0017 (8)	−0.0004 (8)	−0.0023 (8)
C11	0.0329 (12)	0.0302 (11)	0.0273 (10)	−0.0005 (9)	−0.0086 (9)	0.0016 (9)
C17	0.0236 (11)	0.0309 (11)	0.0227 (10)	−0.0034 (9)	0.0005 (9)	0.0013 (8)
C8	0.0258 (11)	0.0237 (9)	0.0197 (9)	−0.0041 (8)	−0.0009 (8)	−0.0026 (7)
C10	0.0363 (12)	0.0287 (10)	0.0193 (9)	−0.0048 (10)	−0.0024 (9)	0.0007 (8)
C6	0.0255 (11)	0.0397 (12)	0.0207 (10)	0.0034 (9)	0.0019 (9)	−0.0028 (9)
C15	0.0209 (10)	0.0257 (10)	0.0213 (10)	−0.0012 (8)	0.0009 (8)	−0.0010 (8)
C9	0.0272 (11)	0.0255 (10)	0.0212 (9)	−0.0043 (8)	0.0018 (9)	−0.0041 (8)
C13	0.0262 (11)	0.0243 (9)	0.0218 (9)	−0.0031 (8)	−0.0015 (8)	−0.0015 (8)
C12	0.0260 (11)	0.0293 (11)	0.0291 (10)	−0.0008 (9)	−0.0026 (9)	0.0009 (9)
C19	0.0235 (11)	0.0340 (11)	0.0229 (10)	0.0016 (9)	−0.0020 (9)	−0.0024 (8)
C18	0.0241 (12)	0.0469 (14)	0.0366 (12)	0.0017 (10)	−0.0020 (10)	−0.0038 (10)
C24	0.0181 (10)	0.0314 (11)	0.0240 (10)	0.0005 (9)	0.0029 (9)	−0.0051 (8)
C22	0.0450 (14)	0.0369 (12)	0.0265 (11)	−0.0045 (11)	0.0109 (10)	0.0016 (9)
C25	0.0561 (17)	0.0359 (12)	0.0275 (11)	−0.0033 (11)	0.0084 (11)	0.0037 (9)
C23	0.0493 (15)	0.0280 (11)	0.0406 (13)	0.0020 (11)	0.0050 (11)	0.0023 (9)
C27	0.0389 (14)	0.0370 (12)	0.0452 (13)	0.0090 (10)	0.0105 (12)	0.0091 (10)
C26	0.0404 (15)	0.0308 (13)	0.0804 (19)	0.0015 (11)	0.0045 (14)	−0.0067 (13)
N2	0.0185 (8)	0.0288 (9)	0.0196 (8)	0.0024 (7)	−0.0006 (7)	−0.0012 (7)
N1	0.0217 (9)	0.0294 (8)	0.0201 (8)	0.0026 (7)	0.0026 (7)	0.0002 (7)
O5	0.0237 (7)	0.0330 (7)	0.0326 (8)	0.0005 (6)	0.0038 (7)	0.0013 (6)
O3	0.0413 (9)	0.0279 (8)	0.0276 (7)	−0.0012 (7)	0.0041 (7)	0.0005 (6)
O2	0.0394 (9)	0.0246 (7)	0.0269 (7)	0.0017 (7)	0.0045 (6)	−0.0020 (5)
O1	0.0348 (9)	0.0368 (8)	0.0215 (7)	−0.0023 (7)	0.0047 (6)	0.0005 (6)
O4	0.0527 (10)	0.0285 (7)	0.0216 (7)	−0.0041 (7)	0.0050 (7)	0.0012 (6)

C3—N2	1.481 (3)	C6—H6B	0.9700
C3—C2	1.500 (3)	C15—H15	0.9800
C3—C14	1.528 (2)	C9—O1	1.375 (2)
C3—H3	0.9800	C13—N1	1.385 (2)
C2—C7	1.359 (3)	C13—C12	1.401 (3)
C2—N1	1.378 (3)	C12—H12	0.9300
C14—C15	1.538 (2)	C19—C18	1.517 (3)
C14—H14A	0.9700	C19—H19A	0.9700
C14—H14B	0.9700	C19—H19B	0.9700
C5—N2	1.479 (2)	C18—H18A	0.9600
C5—C6	1.533 (3)	C18—H18B	0.9600
C5—H5A	0.9700	C18—H18C	0.9600
C5—H5B	0.9700	C24—O3	1.200 (2)
C16—C17	1.334 (3)	C24—O4	1.346 (2)
C16—C24	1.497 (3)	C22—O1	1.434 (2)
C16—C15	1.512 (3)	C22—H22A	0.9600
C21—N2	1.478 (2)	C22—H22B	0.9600
C21—C20	1.530 (3)	C22—H22C	0.9600
C21—H21A	0.9700	C25—O4	1.447 (2)
C21—H21B	0.9700	C25—H25A	0.9600
C20—C19	1.530 (3)	C25—H25B	0.9600
C20—C15	1.553 (3)	C25—H25C	0.9600
C20—H20	0.9800	C23—O2	1.444 (3)
C7—C8	1.435 (3)	C23—H23A	0.9600
C7—C6	1.500 (3)	C23—H23B	0.9600
C11—C12	1.375 (3)	C23—H23C	0.9600
C11—C10	1.408 (3)	C27—O5	1.415 (3)
C11—H11	0.9300	C27—C26	1.495 (4)
C17—O2	1.348 (2)	C27—H27A	0.9700
C17—H17	0.9300	C27—H27B	0.9700
C8—C13	1.403 (3)	C26—H26A	0.9600
C8—C9	1.410 (3)	C26—H26B	0.9600
C10—C9	1.381 (3)	C26—H26C	0.9600
C10—H10	0.9300	N1—H1	0.8600
C6—H6A	0.9700	O5—H5	0.8200
N2—C3—C2	108.46 (15)	O1—C9—C8	115.38 (17)
N2—C3—C14	109.44 (16)	C10—C9—C8	119.27 (18)
C2—C3—C14	114.45 (16)	N1—C13—C12	129.34 (18)
N2—C3—H3	108.1	N1—C13—C8	107.59 (17)
C2—C3—H3	108.1	C12—C13—C8	123.07 (18)
C14—C3—H3	108.1	C11—C12—C13	116.90 (19)
C7—C2—N1	110.71 (16)	C11—C12—H12	121.5
C7—C2—C3	125.74 (18)	C13—C12—H12	121.5
N1—C2—C3	123.47 (17)	C18—C19—C20	114.17 (18)
C3—C14—C15	108.83 (15)	C18—C19—H19A	108.7
C3—C14—H14A	109.9	C20—C19—H19A	108.7
C15—C14—H14A	109.9	C18—C19—H19B	108.7
C3—C14—H14B	109.9	C20—C19—H19B	108.7
C15—C14—H14B	109.9	H19A—C19—H19B	107.6
H14A—C14—H14B	108.3	C19—C18—H18A	109.5
N2—C5—C6	111.38 (16)	C19—C18—H18B	109.5
N2—C5—H5A	109.4	H18A—C18—H18B	109.5
C6—C5—H5A	109.4	C19—C18—H18C	109.5
N2—C5—H5B	109.4	H18A—C18—H18C	109.5
C6—C5—H5B	109.4	H18B—C18—H18C	109.5
H5A—C5—H5B	108.0	O3—C24—O4	122.76 (18)
C17—C16—C24	116.77 (17)	O3—C24—C16	124.37 (17)
C17—C16—C15	129.11 (18)	O4—C24—C16	112.86 (16)
C24—C16—C15	114.11 (16)	O1—C22—H22A	109.5
N2—C21—C20	111.97 (15)	O1—C22—H22B	109.5
N2—C21—H21A	109.2	H22A—C22—H22B	109.5
C20—C21—H21A	109.2	O1—C22—H22C	109.5
N2—C21—H21B	109.2	H22A—C22—H22C	109.5
C20—C21—H21B	109.2	H22B—C22—H22C	109.5
H21A—C21—H21B	107.9	O4—C25—H25A	109.5
C21—C20—C19	113.32 (17)	O4—C25—H25B	109.5
C21—C20—C15	109.77 (16)	H25A—C25—H25B	109.5
C19—C20—C15	112.13 (16)	O4—C25—H25C	109.5
C21—C20—H20	107.1	H25A—C25—H25C	109.5
C19—C20—H20	107.1	H25B—C25—H25C	109.5
C15—C20—H20	107.1	O2—C23—H23A	109.5
C2—C7—C8	106.27 (17)	O2—C23—H23B	109.5
C2—C7—C6	121.23 (18)	H23A—C23—H23B	109.5
C8—C7—C6	132.39 (18)	O2—C23—H23C	109.5
C12—C11—C10	121.73 (19)	H23A—C23—H23C	109.5
C12—C11—H11	119.1	H23B—C23—H23C	109.5
C10—C11—H11	119.1	O5—C27—C26	109.7 (2)
C16—C17—O2	123.94 (18)	O5—C27—H27A	109.7
C16—C17—H17	118.0	C26—C27—H27A	109.7
O2—C17—H17	118.0	O5—C27—H27B	109.7
C13—C8—C9	118.26 (18)	C26—C27—H27B	109.7
C13—C8—C7	107.40 (16)	H27A—C27—H27B	108.2
C9—C8—C7	134.32 (19)	C27—C26—H26A	109.5
C9—C10—C11	120.73 (18)	C27—C26—H26B	109.5
C9—C10—H10	119.6	H26A—C26—H26B	109.5
C11—C10—H10	119.6	C27—C26—H26C	109.5
C7—C6—C5	109.66 (16)	H26A—C26—H26C	109.5
C7—C6—H6A	109.7	H26B—C26—H26C	109.5
C5—C6—H6A	109.7	C21—N2—C5	109.23 (14)
C7—C6—H6B	109.7	C21—N2—C3	107.72 (15)
C5—C6—H6B	109.7	C5—N2—C3	111.39 (15)
H6A—C6—H6B	108.2	C2—N1—C13	108.02 (16)
C16—C15—C14	117.18 (16)	C2—N1—H1	126.0
C16—C15—C20	110.83 (16)	C13—N1—H1	126.0
C14—C15—C20	110.24 (15)	C27—O5—H5	109.5
C16—C15—H15	105.9	C17—O2—C23	113.49 (15)
C14—C15—H15	105.9	C9—O1—C22	116.81 (16)
C20—C15—H15	105.9	C24—O4—C25	114.73 (16)
O1—C9—C10	125.35 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···N2	0.82	2.07	2.876 (2)	169
N1—H1···O5i	0.86	2.01	2.866 (2)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯N2	0.82	2.07	2.876 (2)	169
N1—H1⋯O5i	0.86	2.01	2.866 (2)	170

Symmetry code: (i) .